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Mesoporous Zeolites: Preparation, Characterization and Applications

Javier García-Martínez (Editor), Kunhao Li (Editor), Mark E. Davis (Foreword by)
ISBN: 978-3-527-33574-9
608 pages
May 2015
Mesoporous Zeolites: Preparation, Characterization and Applications (3527335749) cover image


Authored by a top-level team of both academic and industrial researchers in the field, this is an up-to-date review of mesoporous zeolites.
The leading experts cover novel preparation methods that allow for a purpose-oriented fine-tuning of zeolite properties, as well as the related materials, discussing the specific characterization methods and the applications in close relation to each individual preparation approach. The result is a self-contained treatment of the different classes of mesoporous zeolites.
With its academic insights and practical relevance this is a comprehensive handbook for researchers in the field and related areas, as well as for developers from the chemical industry.
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Table of Contents

Foreword XIII

Preface XVII

List of Contributors XXV

1 Strategies to Improve the Accessibility to the Intracrystalline Void of ZeoliteMaterials: Some Chemical Reflections 1
Joaquén Pérez-Pariente and Teresa Álvaro-Münoz

1.1 Introduction 1

1.2 Strategies to Obtain New Large-Pore Materials 5

1.3 Methodologies to Control the Crystallization Process of Zeolite Materials in the Absence of Pore-Forming Agents 9

1.3.1 Confined Nucleation and Growth 11

1.3.2 Use of Blocking Agents for Crystal Growth 13 Silanization Methods 13 Use of Surfactants in the Synthesis of Silicoaluminophosphates 16

1.3.3 Synthesis in the Presence of Pore-Forming Agents 18

1.4 Postsynthesis Methodologies 21

1.4.1 Materials with High Structural Anisotropy: Layered Zeolites 21

1.4.2 Removal/Reorganization of T Atoms in the Crystal Bulk 23

1.5 Conclusions 24

Acknowledgments 25

References 25

2 Zeolite Structures of Nanometer Morphology: Small Dimensions, New Possibilities 31
Heloise de Oliveira Pastore and Dilson Cardoso

2.1 The Structures of Zeolites 34

2.1.1 FAU and EMT Structures: Zeolites X and Y 34

2.1.2 LTA Structure 50

2.1.3 BEA Structure 52

2.1.4 Pentasil Zeolites, MFI, and MEL Structures: ZSM-5, ZSM-11, and S-1 56

2.2 The Structures of Zeotypes: Aluminophosphates and Silicoaluminophosphates 63

2.3 Lamellar Zeolites 66

2.4 Conclusions and Perspectives 71

References 75

3 Nanozeolites and Nanoporous Zeolitic Composites: Synthesis and Applications 79
Gia-Thanh Vuong and Trong-On Do

3.1 Introduction 79

3.2 Synthesis of Nanozeolites 81

3.2.1 Principles 81

3.2.2 Synthesis from Clear Solutions 87 Parameters Affecting the Crystal Size 87

3.2.3 Synthesis Using Growth Inhibitor 90

3.2.4 Confined Space Synthesis 91

3.2.5 Synthesis of Nanozeolites Using Organic Media 95

3.3 Nanozeolite Composites 98

3.4 Recent Advances in Application of Nanozeolites 106

3.5 Conclusions and Perspectives 109

References 110

4 Mesostructured and Mesoporous Aluminosilicates with Improved Stability and Catalytic Activities 115
Yu Liu

4.1 Introduction 115

4.2 Zeolite/Mesoporous Composite Aluminosilicates 116

4.2.1 Synthesis of Zeolite/Mesoporous Composite Material 116

4.2.2 Catalytic Evaluation of Zeolite/Mesoporous Composite Material 124

4.3 Posttreatment of Mesostructured Materials 128

4.3.1 Posttreatment of Mesoporous Materials by Zeolite Structure-Directing Agents or Zeolite Nanocrystals 128

4.3.2 Postsynthesis Grafting of Aluminum Salts on theWalls of Mesostructured Materials 133

4.4 Mesostructured and Mesoporous Aluminosilicates Assembled from Digested Zeolite Crystals 135

4.5 Mesostructured and Mesoporous Aluminosilicates Assembled from Zeolite Seeds/Nanoclusters 141

4.5.1 Assembly of Mesostructured Aluminosilicates from Zeolite Y Seeds 141

4.5.2 Assembly of Mesostructured Aluminosilicates from Pentasil Zeolite Seeds 145

4.6 Conclusions 152

References 153

5 Development of Hierarchical Porosity in Zeolites by Using Organosilane-Based Strategies 157
David P. Serrano, José M. Escola, and Patricia Pizarro

5.1 Introduction 157

5.2 Types of Silanization-Based Methods 159

5.2.1 Functionalization of Protozeolitic Units with Organosilanes 159 Fundamentals of the Method 159 Influence of the Organosilane Type 163 Application to Different Zeolites 166 Influence of the Silica Source 168 Reduction of the Gel Viscosity by Means of Alcohols 169 State of the Aluminum and Acidity 171

5.2.2 Use of Silylated Polymers 173

5.2.3 Use of Amphiphile Organosilanes 175

5.3 Catalytic Applications 180

5.3.1 Fine Chemistry 180

5.3.2 Oil Refining and Petrochemistry 185

5.3.3 Production of Advanced Fuels 189

5.4 Conclusions 193

5.5 New Trends and Future Perspectives 195

References 196

6 Mesoporous Zeolite Templated from Polymers 199
Xiangju Meng and Feng-Shou Xiao

6.1 Introduction 199

6.2 Cationic Polymer Templating 200

6.3 Nonionic Polymer Templating 203

6.4 Silane-Functionalized Polymer Templating 208

6.5 Polymer–Surfactant Complex Templating 210

6.6 Morphology Control of Mesoporous Zeolites Using Polymers 212

6.7 Zeolites with Oriented Mesoporous Channels 218

6.8 Microfluidic Synthesis of Mesoporous Zeolites 220

6.9 Nonsurfactant Cationic Polymer as a Dual-Function Template 220

6.10 Conclusions 224

References 224

7 Nanofabrication of Hierarchical Zeolites in Confined Space 227
Zhuopeng Wang and Wei Fan

7.1 Introduction of Confined Space Synthesis 227

7.2 General Principles of Confined Space Synthesis 228

7.3 Crystallization Mechanisms of Zeolite under Hydrothermal Conditions 228

7.4 Preparation of Synthesis Gel within the Confined Space of Inert Matrices 230

7.5 Crystallization of Zeolite within Confined Space 230

7.6 Synthesis of Hierarchical Zeolites in Carbon Blacks, Nanotubes, and Nanofibers by SAC Method 232

7.7 Synthesis of Hierarchical Zeolites within Ordered Mesoporous Carbons by SAC and VPTMethods 234

7.8 Synthesis of Hierarchical Zeolites within Carbon Aerogels, Polymer Aerogels, and other Carbon Materials 241

7.9 Synthesis of Hierarchical Zeolites within Carbon Materials Using Seeded Growth Method 243

7.10 Confined Synthesis of Zeolites in Polymer and Microemulsions 248

7.11 Conclusions 250

References 253

8 Development of Hierarchical Pore Systems for Zeolite Catalysts 259
Masaru Ogura and Masahiko Matsukata

8.1 Introduction 259

8.2 Alkali Treatment of ZSM-5: Effects of Alkaline Concentration, Treatment Temperature, and Treatment Duration 260

8.3 Desilication of ZSM-5: Effects of Temperature and Time 263

8.4 Alkali Treatment of ZSM-5 with Various Si/Al Molar Ratios: Effect of Si/Al on Mesopore Formation 263

8.5 Desilication of ZSM-5: Effects of Other Descriptors 272

8.6 Desilication of Silicalite-1 273

8.7 Desilication of Other Zeolites: Multidimensionalization of Low-Dimensional Microstructures 277

8.8 Desilicated Zeolites for Applications – Test Reactions 280

8.9 Desilicated Zeolites for Applications – Superior Diffusion 284

8.10 Desilicated Zeolites for Novel Applications 289

8.11 Summary 291

References 292

9 Design and Catalytic Implementation of Hierarchical Micro–Mesoporous Materials Obtained by Surfactant-Mediated Zeolite Recrystallization 295
Irina I. Ivanova, Elena E. Knyazeva, and Angelina A. Maerle

9.1 Introduction 295

9.2 Mechanism of Zeolite Recrystallization 296

9.3 Synthetic Strategies Leading to Different Types of Recrystallized Materials 301

9.4 Coated Mesoporous Zeolites (RZEO-1) 303

9.5 Micro–Mesoporous Nanocomposites (RZEO-2) 308

9.6 Mesoporous Materials with Zeolitic Fragments in theWalls (RZEO-3) 312

9.7 Conclusions 316

Acknowledgment 318

References 318

10 Surfactant-Templated Mesostructuring of Zeolites: FromDiscovery to Commercialization 321
Kunhao Li,Michael Beaver, Barry Speronello, and Javier García-Martínez

10.1 Introduction 321

10.2 Surfactant-Templated Mesostructuring of Zeolites 326

10.3 Mesostructured Zeolite Y for Fluid Catalytic Cracking Applications 334

10.4 Beyond Catalysis: Mesostructured Zeolite X for Adsorptive Separations 341

10.5 Concluding Remarks 344

References 345

11 Physical Adsorption Characterization of Mesoporous Zeolites 349
Matthias Thommes, Rémy Guillet-Nicolas, and Katie A. Cychosz

11.1 Introduction 349

11.2 Experimental Aspects 352

11.2.1 General 352

11.2.2 Choice of Adsorptive 354

11.3 Adsorption Mechanism 357

11.4 Surface Area, Pore Volume, and Pore Size Analysis 363

11.4.1 Surface Area 363

11.4.2 Pore Size Analysis 367 General Aspects 367 Pore Size Analysis: Hierarchically Structured Materials 370

11.5 Probing Hierarchy and Pore Connectivity in Mesoporous Zeolites 376

11.6 Summary and Conclusions 378

References 379

12 Measuring Mass Transport in Hierarchical Pore Systems 385
Jörg Kärger, Rustem Valiullin, Dirk Enke, and Roger Gläser

12.1 Types of Pore Space Hierarchies in Nanoporous Host Materials 385

12.2 Hierarchy of Mass Transfer Parameters and Options of Their Measurement Techniques 389

12.2.1 Diffusion Fundamentals 389

12.2.2 Techniques of Diffusion Measurement 392 Macroscopic Diffusion Studies: Uptake and Release 392 Microscopic Diffusion Measurement: Molecular Displacements 396 Microscopic Diffusion Measurement: Transient Concentration Profiles 399

12.3 Diffusion Measurement in Various Types of Pore Space Hierarchies 400

12.3.1 Macro/Meso 400

12.3.2 Macro/Micro 401

12.3.3 Meso/Meso 404

12.3.4 Meso/Micro 407 PFG NMR DiffusionMeasurements in Y-Type Zeolites: A Case Study with FCC Catalysts 407 Mass Transfer in Mesoporous LTA-Type Zeolites: An In-Depth Study of Diffusion Phenomena in Mesoporous Zeolites 409 Diffusion Studies with Mesoporous Zeolite of Structure-Type CHA: Breakdown of the Fast-Exchange Model 414 The Impact of Hysteresis 415

12.4 Conclusions and Outlook 416

References 417

13 Structural Characterization of Zeolites and Mesoporous Zeolite Materials by ElectronMicroscopy 425
Wei Wan, Changhong Xiao, and Xiaodong Zou

13.1 Introduction 425

13.2 Characterization of Zeolites by Electron Diffraction 426

13.2.1 Geometry of Electron Diffraction 427

13.2.2 Conventional Electron Diffraction 428

13.2.3 Three-Dimensional (3D) Electron Diffraction 430

13.3 Characterization of Zeolite and Mesoporous Materials by High-Resolution Transmission Electron Microscopy 433

13.3.1 Introduction to HRTEM 433

13.3.2 Working with Electron-Beam-Sensitive Materials 434

13.3.3 Structure Projection Reconstruction from Through-Focus HRTEM Images 435

13.3.4 3D Reconstruction of HRTEM Images 437

13.4 Characterization of Zeolite and Mesoporous Materials by Electron Tomography (ET) 440

13.4.1 Basic Principles of Electron Tomography 440

13.4.2 Applications of Electron Tomography on Mesoporous Zeolites 443 Quantification of Mesopores in Zeolite Y 443 Quantification of Pt Nanoparticles in Mesoporous Zeolite Y 444 Orientation Relationship between the Intrinsic Micropores of Zeolite Y andMesopore Structures 445 Single-Crystal Mesoporous Zeolite Beta Studied by Transmission Scanning Electron Microscopy (STEM) 448

13.5 Other Types of Mesoporous Zeolites Studied by EM 450

13.5.1 Aluminosilicate Zeolite ZSM-5 Single Crystals with b-Axis-Aligned Mesopores 450

13.5.2 Mesoporous Zeolite LTA 451

13.5.3 Ultrasmall EMT Crystals with Intercrystalline Mesopores from Organic Template-Free Synthesis 452

13.5.4 Self-Pillared Zeolites with Interconnected Micropores and Mesopores 452

13.6 Future Perspectives 454

13.7 Conclusions 455

Acknowledgments 456

References 456

14 Acidic Properties of Hierarchical Zeolites 461
Jerzy Datka, Karolina Tarach, and Kinga Góra-Marek

14.1 Short Overview of Experimental Methods Employed for Acidity Investigations 461

14.2 Hierarchical Zeolites Obtained by Templating and Dealumination of Composite Materials 463

14.2.1 Surfactant Templating Approach 465

14.2.2 Dealumination 470

14.3 Hierarchical Zeolites Obtained by Desilication 471

14.3.1 Studies of Desilicated Zeolites Acidity 471 Analysis of the Hydroxyl Groups Spectra 471 Concentration of Acid Sites 474 Studies of Acid Sites Strength 475 Realumination: Mesopore Surface Enrichment in Al Species 476 Nature and Origin of Lewis Acid Sites in Desilicated Zeolites 477

14.3.2 Accessibility of Acid Sites in Desilicated Zeolites 481

14.4 Conclusions and Future Perspectives 487

Acknowledgments 489

References 489

15 Mesoporous Zeolite Catalysts for Biomass Conversion to Fuels and Chemicals 497
Kostas S. Triantafyllidis, Eleni F. Iliopoulou, Stamatia A. Karakoulia, Christos K. Nitsos, and Angelos A. Lappas

15.1 Introduction to Mesoporous/Hierarchical Zeolites 497

15.2 Potential of Hierarchical Zeolites as Catalysts for the Production of Renewable/Biomass-Derived Fuels and Chemicals 503

15.3 Catalytic Fast Pyrolysis (CFP) of Lignocellulosic Biomass 508

15.4 Catalytic Cracking of Vegetable Oils 514

15.5 Hydroprocessing of Biomass-Derived Feeds 516

15.6 Methanol to Hydrocarbons 524

15.6.1 Methanol to Dimethyl Ether (DME) 525

15.6.2 Methanol to Gasoline (MTG)/Methanol to Olefins (MTO) 527

15.7 Other Processes 533

15.8 Summary and Outlook 535

References 536

16 Industrial Perspectives for Mesoporous Zeolites 541
Roberto Millini and Giuseppe Bellussi

16.1 Introduction 541

16.2 Enhancing the Effectiveness of the Zeolite Catalysts 543

16.2.1 Increasing the Pore Size 544

16.2.2 Hierarchical (Mesoporous) Zeolites 546

16.3 Industrial Assessment of Mesoporous Zeolite 555

16.4 Conclusions 560

References 561

Index 565

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Author Information

Javier García-Martínez is the founder of and chief scientist at Rive Technology, Inc. in Boston, USA, a spin-off from MIT that commercializes mesostructured zeolites to the refining industry. He is also Professor of Inorganic Chemistry and the director of the Molecular Nanotechnology Lab at the University of Alicante, Spain. Since 2011 he is a member of the Bureau of IUPAC and Fellow of the Royal Society of Chemistry. His work has been honored with the European Young Chemist Award in 2006, MIT's Technology Review Award (TR35) in 2007, and by the World Economic Forum, which selected him as a Young Global Leader in 2009. Professor García-Martínez has published extensively in the areas of nanomaterials, catalysis, and energy, and also has over 25 patents to his name. His latest books are "Nanotechnology for the Energy Challenge" (Wiley-VCH, 2014) and "The Chemical Element" (Wiley-VCH, 2011).

Kunhao Li is a Project Leader at Rive Technology, Inc. since 2008. He has been heavily involved in the improvement of Rive's core technology in zeolite mesostructuring processes, zeolites and catalysts characterization, testing, and evaluation, as well as extension of application areas of mesostructured zeolites to chemical separations and other catalytic processes. He obtained PhD in chemistry at The George Washington University and did postdoctoral research at Rutgers University. His research work has resulted in many publications in the form of original papers and reviews, book chapters, technical reports, patent applications, and patents.
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'This book is interesting and very informative. It broadly covers all areas of mesoporous materials: synthesis, characterisation and application.' (Johnson Matthey Process Technology 2016)
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